Lubricant and hydrocarbon fuel compositions

ABSTRACT

The stability and cleanliness of lubricating oils under severe thermal and oxidative conditions are improved and the electrical conductivity of hydrocarbon fuels is increased by adding thereto a copolymer of cetyl vinyl ether and N-vinyl-pyrrolidone.

United States Patent Frangaws [451 July 11, 1972 |s4| LUBRICANT ANDHYDROCARBON 3.141.222 9/1964 Bauer ..44/63 FUEL COMPOSITIONS PrimaryExaminer-Daniel E. Wyman [72] Inventor: Gerasslmos Frangatos, Westmont,NJ. Assistant Examiner-Mrs. Y. H. Smith Attorney-Oswald G. Hayes, AndrewL. Gaboriault, Raymond [73] Asslgnee' oncwpmu w. Barclay and Claude E.Setliff [22] Filed: June 19, 1970 21 Appl. No.: 47,900 [571 ABSTRACT Thestability and cleanliness of lubricating oils under severe thermal andoxidative conditions are improved and the electrical conductivity ofhydrocarbon fuels is increased by adding [58] Field or e a i..............II4Z}63 62-252751 SR 403 harem a vinyl ether and Yrolidone. [56] References Cited UNITED STATES PATENTS 15 Claims, NoDrawings 3,506,574 4/1970 Stambaugh at al. ..44/63 BACKGROUND OF THEINVENTION 1. Field of the Invention This invention, in one of itsaspects, relates to organic liquids having desirable anti-staticproperties. In this aspect, the invention relates more particularly toorganic liquid compositions in the form of volatile organic liquids suchas hydrocarbon fuels or solvents which possess low electricalconductivity which, when they accumulate electrostatic charges, may giverise to the hazards of ignition or explosion. in another of its aspects,the invention relates to lubricants having improved stability andcleanliness. More particularly with regard to both aspects, theinvention relates to the improvement of such organic liquids andlubricants by incorporating therein additives which are eflective inincreasing the electrical conductivity of such liquids and in improvingoxidative stability and cleanliness of such lubricants.

2. Description of the Prior Art Prior to the present invention, the lowelectrical conductivity of many volatile organic liquid compositions haspresented the problem of controlling static buildup, particularly duringhandling and transportation, for the purpose of insuring safe andeffective distribution without the concomitant danger of ignition orexplosion. For example, volatile organic liquids such as hydrocarbonfuel oils (e.g., gasoline, jet fuels, turbine fuels and the like), orlight hydrocarbon oils employed for such purposes as solvents orcleaning fluids for textiles, possess a very low degree of electricalconductivity. In the use of such fluids, electrostatic charges, whichmay be generated by handling, operation or other means, tend to form onthe surface, and may result in sparks, thus resulting in ignition orexplosion. These hazards may be encountered merely in the handling ortransportation of such organic liquids and even in operations, such ascentrifuging, in which a solid is separated from a volatile liquid,during which electrostatic charges can accumulate.

Various materials have heretofore been proposed for incorporation intosuch organic liquid compositions for increasing their electricalconductivity and thus reduce the aforementioned dangers of ignition andexplosion. Such materials, however, have not been proved to besufficiently efl'ective in increasing the desired electricalconductivity of these fluids and, in many instances, have been'found tobe too costly for the relatively small degree of increased protectionwhich they are capable of providing.

Lubricating oils are subject to oxidative deterioration at elevatedtemperatures or upon prolonged exposure to the elements. Theselubricants, including mineral oils and synthetic oils, undergo oxidativedeterioration in service, especially at high temperatures. Thisdeterioration produces sludges and gums, causes metal parts to corrodeand produces loss of lubricating properties of the oil. Many additivesof the prior art are only marginally effective except at highconcentrations, especially when the oils are subjected to drasticoxidizing conditions.

SUMMARY OF THE INVENTION In accordance with the present invention thereare provided lubricating oil and hydrocarbon fuel compositionscomprising a major amount of said oil or fuel and an amount sufficientto improve the properties thereof of a copolymer of cetyl vinyl etherand N-vinylpyrrolidone.

DESCRIPTION OF SPECIFIC EMBODIMENTS The "preparation of theaforementioned cetyl vinyl ether-N- vinylpyrrolidone copolymer may beconducted at molar ratios of the monomers of from 1:1 to about :1, i.e.,either can vary within this range. It is believed that the structure ofthe copolymer will conform to the following recurring units where n mayvary from 2 to 200. The composition of the copolymer corresponds to thecomposition of the monomer mixture of the feed.

In general, the invention contemplates the use of from about 000001percent to about 15 percent of the additive by weight of the fluidsdisclosed herein. Preferably, the concentration of co-polymer inlubrication oils will be from about 0.01 to about 10 percent by weightthereof, more preferably from about 0.1 percent to about 5 percent. Inhydrocarbon fuels, its concentration will be preferably within the rangeof from about 0.000025 percent to about 0.05 percent by weight thereof.Expressed in another way for the hydrocarbon fuel, the overall rangewill be from about 0.1 lb. to about 200 lbs. per 1,000 barrels of fuel,and the most preferred will range from about 1 pound to about 10 poundsper 1,000 barrels.

A field of specific applicability of the present invention is in theimprovement of organic liquid compositions in the form of petroleumdistillate fuel oils having an initial boiling point from about 75 F. toabout F. and an end boiling point from about 250 F. to about l,000 F. Itshould be noted, in this respect, that the term distillate fuel oils isnot intended to be restricted to straight-run distillate fractions.These distillate fuel oils can be straight-run distillate fuel oils,catalytically or thermally cracked (including hydrocracked) distillatefuel oils, or mixtures of straight-run distillate fuel oils, napthas andthe like, with cracked distillate stocks. Moreover, such fuel oils canbe treated in accordance with well-known commercial methods, such asacid or caustic treatment, hydrogenation, solvent refining, claytreatment, and the like.

The distillate fuel oils are characterized by their relatively lowviscosity, pour point and the like. The principal property whichcharacterizes their contemplated hydrocarbons, however, is theirdistillation range. As hereinbefore indicated, this range will liebetween about 75 F. and about l,000 F. Obviously, the distillation rangeof each individual fuel oil will cover a narrower boiling range, fallingnevertheless, within the above-specified limits. Likewise, each fuel oilwill boil substantially, continuously, throughout its distillationrange.

Particularly contemplated among the fuel oils are Nos. 1, and 3 fueloils, used in heating and as Diesel fuel oils, gasoline, turbine fuelsand the jet combustion fuels, as previously indicated. The domestic fueloils generally conform to the specifications set forth in ASTMSpecification D396-48T. Specifications for Diesel fuels are defined inASTM Specification D975-48T. Typical jet fuels are defined in MilitarySpecification MILF5624B.

The lubricants which may be improved by the addition thereto of theabove-mentioned copolymer are mineral oils, both paraffinic andnaphthenic, and synthetic oils. The synthetic oils include polyolefinfluids, polyglycols, polyacetals, the siloxanes and the like. Especiallyuseful are those synthetic esters which are becoming more and morepopular, particularly in aviation. These include esters made frompolycarboxylic acids and monohydric alcohols or from polyhydric alcoholsand monocarboxylic acids. Of these the most preferred members are thosemade from pentaerythritol, or mixtures thereof with di -andtripentaerythritol, and an aliphatic monocarboxylic acid containing from1 to about 20 carbon atoms or a mixture of such acids.

In broad aspect, the copolymer is prepared by mixing the monomers in amutual solvent therefor, adding a free radical initiator and heating,preferably at reflux, for the time required to effect the reaction.

Any of the well-known solvents may be used in the synthesis of thecopolymer. One such solvent is chlorobenzene. Others will immediatelybecome evident to one skilled in this art, so there is no need forlisting them here. These may be selected so that the reaction can beconducted within the range of from about 75 C. to about 250 C.,preferably from about 100 C. to about 175 C.

Any of the commonly used initiators may be used. Most common amongthese, and the ones preferred in the practice of this invention, are theperoxides and the hydroperoxides. Some examples of these are ditertiarybutyl peroxide, dicumyl peroxide, azoisobutyronitrile, dilaurylperoxide, diacetyl peroxide, tertiary butyl hydroperoxide, cumylhydroperoxide and percarbonate esters.

The following examples will serve to illustrate the preparation of thecopolymers and their use as antistatic and stability agents.

EXAMPLE 1 Into a reactor was placed 300 ml. of chlorobenzene and 5 gramsof ditertiary butyl peroxide was added thereto. The solution was broughtto reflux temperature (about 130 C.) and a mixture of 107.2 grams (0.4mole) of cetyl vinyl ether, 44.4 grams (0.4 mole) of n-vinylpyrrolidoneand 100 ml. of chlorobenzene was added to the solution over a period of45 minutes. Refluxing was continued for 2 hours. The reaction mixturewas cooled and left under N pressure overnight.

Two additional grams of ditertiary butyl peroxide were added, thereaction mixture was brought to reflux and was held there for 6 hours.The solvent and unreacted monomer were removed in vacuo (0.3 mm of Hg)at 200 C. for 1 hour. The product (124 grams) was an amber coloredfluid, which solidified on cooling.

EXAMPLE 2 Evaluation of Products a. Anti-Static Tests In HydrocarbonFuel 1n obtaining the data for the following table comparativeelectrical conductivity tests were carried out for the purpose ofdetermining the aforementioned property of the Example 1 composition.The test employed for this purpose was electrical conductivity measuredin picomhos (i.e. 10 mhos) per meter. In these tests the agent wasblended in a liquid hydrocarbon fuel having a boiling range of 300500 F.It was a kerosine of predominantly parafiinic composition, i.e., from90-95 percent. The resulting fuel composition was evaluated for thedegree of improvement in electrical conductivity, as shown in the table.

The startling effect the polymer of Example 1 has on the fuel oil isevident from Table 1. Even at 1.25 pounds he polymer raises theconductivity by a factor of 5. Thus it may be seen that such polymer isan important antistatic agent.

b. Oxidation Test In Synthetic Ester Lubricant The compounds produced inaccordance with this invention were blended into a synthetic ester oillubricant and tested in an oxidation test in accordance with thefollowing procedure.

A sample of the test composition is heated to 450 F. and air at the rateof about 5 liters per hour is passed through for a period of about 24hours. Present in the test sample are specimens of iron, copper,aluminum, and lead. The kinematic viscosity is measured at 100 F. KVchange) and the change in the neutralization number (NN change). Itshould be noted that the metals are typical metals of engine or machineconstruction, and they also lplrovide some catalysis for the oxidationof organic materials. e results, tabulated in Table 2, concern theproduct of Example 1.

Synthetic ester made from pentaerythritol and an equimolar mixture of Cand C monocarboxylic acids. It contains about 5 percent of an additivepackage comprising a major amount of a neutral phosphate ester andlesser amounts ofan amine mixture and a metal suppressor as well asabout 0.3 percent ofbis(nonylphenyl) phosphonate.

Iclaim:

1. An organic fluid composition comprising a fluid selected from thegroup consisting of lubricating oils and hydrocarbon fuels and fromabout 0.00001 percent to about 15 percent by weight thereof of acopolymer of cetyl vinyl ether and N-vinylpyrrolidone.

2. The composition of claim 1 wherein said copolymer is present in anamount of from about 0.00001 percent to about 15 percent by weight ofsaid fluid.

3. The composition of claim 1 wherein the copolymer is prepared in thepresence of a free-radical initiator.

4. The composition of claim 3 wherein the free radical initiator isditertiary butyl peroxide.

5. The composition of claim I wherein said hydrocarbon fuel comprises apetroleum distillate fuel oil having an initial boiling point from about75 F. to about 135 F. and an end boiling point from about 250 F. toabout 1,000 F.

6. The composition of claim 1 wherein hydrocarbon fuel is gasoline.

7. The composition of claim 1 wherein said hydrocarbon fuel is ajetfuel.

8. The composition of claim 1 wherein said hydrocarbon fuel is a turbinefuel.

9. The composition of claim 7 wherein said jet fuel has a boiling rangeof 300500 F. and is a kerosine having from about percent to aboutpercent paraffin content.

10. The composition of claim 5 wherein the copolymer is present in saidfuel within the range of from about 0.1 to about 200 pounds per thousandbarrels thereof.

11. The composition of claim 10 wherein the said range is from about 1to about 10 pounds per thousand barrels of said fuel.

12. The composition of claim 1 wherein said lubricating oil is apentaerythritol ester.

13. The composition of claim 12 wherein said ester is prepared frompentaerythritol and a monocarboxylic acid having from about 1 to about20 carbon atoms or mixtures thereof.

14. The composition of claim 13 wherein the mixed acid is a mixture ofacids having from 5 to 9 carbon atoms.

15. The composition of claim 12 wherein the copolymer is present withinthe range of about 0.01 percent to about 10 percent by weight of theester.

*zgygg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3A7 Dated July 1972 v Inventofls) Gerassimos Frangatos It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

In column 4, Table 2, should appear as follows: w

. Ini- Ini- 1118.1 Final tial Final A KV Oil Additive NN N'N ANN KV KVA* o 0.30 6.90 6.60 27.37 5o. +8 8 mm Signed and sealed this 6th day ofFebruary 1973.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. ROBERT GOTTSCHALK Commissioner of PatentsAttesting Officer

3. The composition of claim 2 wherein the free radical initiator isditertiary butyl peroxide.
 4. The composition of claim 1 wherein saidhydrocarbon fuel comprises a petroleum distillate fuel oil having aninitial boiling point from about 75*F. to about 135* F. and anendboiling point from about 250* F. to about 1,000* F.
 5. The compositionof claim 1 whereinydrocarbon fuel is gasoline.
 6. The compositionf claim1 wherein said hydrocarbon fuel is a jet fuel.
 7. The composition ofclaim 1 wherein said hydrocarbon fuel is a turbine fuel.
 8. Thecomposition of claim 6 wherein said jet fuel has a boiling range of300*- 500* F. andis a kerosine having from about 90 per cent to about 95per cent paraffin content.
 9. The composion of claim 4 wherein thecopolymer is present in said fuel within the range of from abox 0.1 toabout 200 pounds p thousand barrels thereof.
 10. The composition of clim9wherein the said range is from abou1 to about 10 pounds per thousandbarels of said fuel.
 11. The composition of claim 1 wherein saidlubricating oil is a pentaerythritol ester.
 12. The composition of claim1wherein said ester is prepared from pentaerythritol and amonocarboxylic acid having from about oneto 20 carbon atoms or mixturesthereof.
 13. The composition of claim 12 wherein the mixed acid is amixture of acids having from five to nine carbon atoms.
 14. Thecomposition of claim 11 wherein the copolymer is present within therange of about 0.01 per cent to about 10 per cent by weight of theester.
 15. The composition of claim 12 wherein the copolymer is presentwithin the range of about 0.01 percent to about 10 percent by weight ofthe ester.